Method of making zinc sulphide



July 27 1926.

F. G. BREYER ET AL METHOD OF MAKING ZINC' SULPHIDE Filed April 7, 1925 INVENTORS mcm i I ATTORNEYS Patented ay 27, 192%,

S AT PATENT; OFFICE; 1'

rnnrx e. ranxna, or rnnnnaron, AND cmyms 'w. EA-BBER, or nowmms'rown,

PENNSYLVANIA, ASSIGNORSJTO THE NEW JERSEYZINC COMPANY, OF NEW YORK,

N'. Y., CORPORATION 01? .NEW JERSEY.

Earner or meme zmc sunrnmn,

Application med-4pm- 1, 1525. Serial m. 21,277..

This inventionrelates to zinc pigment and has for its object the provision,

of an improved method of making zinc sulphide in, the form of a pigment. When a mixture of zinc oxide pigment and sulphur is heated under non-oxidizing conditions, as for example in a closed vessel, to. a temperature in excess of about 400? 0., a reaction readily takes place between the zinc oxide and sulphur resulting in the formation of zinc sulphide of appropriate physical characteristics foruseas a pigment. .The chemical' reaction may be represented by the following equation:

The reaction between the zinc oxide. pig-- fmen,t and sulphur begins at a temperature slightly above 100 C. The reaction velocity increases with rise in temperature be-' .1

taining approximately the calculated theof retical proportion of zinc oxide and sulphur. This appears to be due in part to loss of sulphur by volatilization from the charge, the vapor tension or: sulphur being'hi'gh .at

these temperatures so that considerable sul v phur vapor is carried away with the sulphur,

ioxide gas resulting from the reaction.

a consequence of volatilization may be overcome by using an appropriate. excess of sulphur in the mixture. Practically conipl te zi nc better gradesrof white pigments.

" Our present invention involves an" im-.

conversion of the zinc oxide pigment to sulphide pigment can be accomplished at a temperature of 450 6. witha mixture containing more than the calculated proportion of sulphur and azinc foxide pig-- ment of relatively small particle" size. In'-.

crease of-the vtemperature to 600 C. and higher correspondingly increases the reaction velocity and gives more consistently high conversion of zinc oxide to,zinc-v sulphide.

The

fineness of particle subdivision of the zinc oxide igment exercises a: marked influence on t e rapiditywith which the 're'aetion proceeds and its degree of completeness. Thus, with the usual grades of American or French process oxide, whose sired having the maximum ness and brightness, it is essential that only ra' id 0.4-0.5 micron, the. reaction proceeds relatively much slower thanwith zinc oxide of an average; particle size of 0.25 micron,-or'

less, such as described in the 'United- States average 5 particle size j is approximately 1 patent of Breyer, Gaskill and Singmaste'r, y

ment is effected when using zin'coxide pig ment of an average, particle size "of .025

micron oraless. ,1 Y

If'a zine sulphide pigment product is depossible whiteextremely pure zincoxide and sulphur be used. The most satisfactory zincox dejp'igment this respect isthat made from high grade slab zinc. Similarly, resublimed flow-L ers of sulphur should be used. -The"zinc; sulphide pigment made from less purezinc oxide and sulphur is usually deficient in color' and brightness. If these properties of color and brightness are notof the' first importance,"lower gradera'w materials may.

be used.

' The zine sulphide pigment obtained: by heating a mixture- 0f zinc oxide pigment and sulphur, in the manner hereinbefore described,.is a-yellowish whitepowden-hav- I I 'ing; no visible crystalline character, .even This deficiency of sulphur inv-the charge as whenexamined-underthe highest.magnification with themicroscope- It has good pigment properties when rubbeddownv in oil but its. color is more yellow than the;

proved method of carrying out the [heat treatment of a mixture of zinc .oxide .pigment andsulphurfor the production ofa pigment composed tor themost pargof zinc sulphide. In accordance'with the present invention, the mixture of "zinc oxide pigment and sulphur is progressively passed through. an upright reaction chamber and whilepass in'g through the chamber is sub- The reaction chamber is preferably an upright or; vertically disposed retort external y heated to a. temperatureof approximately 'jected' to asufli'cien'tly high temperature to efi'ect the ready formation of zinc sulphide.

of the. mixture or zinc oxide pigment and sulphur, substantially fills the upright reaction chamber or' -retort and passes by gravity therethrough. The resulting product' is progressively discharged from the bottom of the chamber or retort and is cooled under conditions inhibiting any'appreciable' oxidation of the zinc sulphide therein.

In accordance with our' preferred practice, the upright chamber or retort is operated so as to subject the charge progressively passing therethrough to a two-stage heattreatment operation in "the first stage of.

which substantially complete conversion of a zinc oxide to zinc sulphide is eflictedandin the second stage of which an improvement in the color of the zinc sulphide'is attained. The mixture of zinc oxide pigment and sulphur is charged into the top of the upright chamber or retort and progresses downwardly therethrough as fast asthe finished product is withdrawn from the bottom. The

mixture first passes through a heated zone' "where the temperature is irapidly raised to a point at which the reaction between thezinc oxide and sulphur readily proceeds.

Below this reaction zone, the charge (now crude zinc sulphide) passes into a second heated zone-in which the temperature may be controlled independently of the temperature in the reaction 'zone .In this second heated zone the charge is subjected 13073 temperature usually slightly lower than the temperature in the reaction zone,. and as a result of this heat treatment an improvement in the color ofthe product is attained.

Thesecond heated zone ispreferably followed by a cooling zone through which the charge progresses and from which the finished product is withdrawn in any approppiate manner. Careshould be taken to cool the finishedproduct to a temperature below that at which oxidation of zinc sulphide takes place (about LOO-450 C.) under nonoxidizlng conditions.

In the single figure of the accompanying' drawing, we have illustrated an apparatus particularly adapted for carrying out the present invention.

The apparatus illustrated in the drawing comprises a firebox5 having a grate 6, a

firing door 7 with a counter-weighted. closure 8 therefor, and ash-pit 9. A flue 10 conducts the gaseous products of combustion from the re box to the retort or mufile chamber 11. An u right or vertically dis- Y posed retort or mu e 12-is mounted within" .thechamber 11. ,Where the apparatus is to carry out the aforementioned two-stage heat-treatment operation the retort 12 may conveniently be a zincrcoated steel pipe about 9 inches in diameter and about 30 feet long.

The gaseous products of combustion from the burning fuel on the grate 6 pass through the flue 10 into't-he chamber 11 and surround the retort 12 and escape from the top of thechamber 11 through an opening 13 to an appropriate stack (not shown).

The furnace structure of the heating Appropriate dampers 15 may be provided t'or' proportioning the relative amounts of I the fire gases admitted to the two points of the heating chamber ll.

The retort 12 isprovided at its upper end with an extension 12. 'The mixed zincoxide and sulphur is charged into the lower end of the extension 12 through a hopper 16 and a screw conveyor-17. The upper portion of the extension 12' serves as a stack for the escape of the gaseousproducts resulting from the interaction of the zinc.

oxide and sulphur. If desired, the extension 12 may be connected by suitable fiues to a sulphuric acidplant for the recovery of the sulphurdioxide gas. A rapping mechanism 18 is provided for periodically striking the extension '12 and thereby preventing the.

bridging andhangi-ng of the charge in the mufile tube'or retort 12.

The lower end ofthe retort 12 communicates with an extension 12 exposed to the [atmosphere below the furnace structure of the muflie chamber. The extension 12" is provided with a mechanically actuated star wheel discharge 19. The extension 12 terpan. 20 where an effective seal 'is provided by the accumulation of thed-ischa-rged sulphide in the pan. The cover of the pan 20 1s provided with ahinged portion 20: per mitting convenient access to the interior of the pan for leveling the material therein or for removing material therefrom.

The actual practice of the invention will be better understood from the following description representing what we now consider the preferred manner of carrying out the invention. t

. Zinc oxide (preferably of a particle size of about 0.25 micron oriless and carrying" less than 0.1% of combined lead, cadmium;

and iron oxides or other impurities which would yield dark-colored sulphides) .is

mixed with about three quarters of its weight of finely divided sulphur, preferablyresublimed flowers of sulphur of highpu rity. This proportion includes an excess of 25% over the chemically equivalent propor-v tion of sulphur to allow for volatilization losses. .The proportions of zinc oxide and I sulphur should be such as to supply sufiieientinmates at its lower end within acovered i -the burning fuel in the fire box.

I 55 of about 675-7005 in the lower half of zat-ionlosses; x l The mixing of the zinc oxide and sulphur should be carried out in such a way as to 5 avoid compa'cting of the charge. :A-SatiS factory form of mixture is a rOtaryscreen of the type used forjbolting zinc oxide with a screen of about 14 meshesper linealinch,

' Usually'two passes through the screen are mixture.v 1

Failure to provide -a suflicient excess of sulphur or to avoid compacting f of 'the charge during-mixing ofthe zinc oxide and 15 sulphur may result. in low conversion of the zinc oxide to zinc sulphide.

The mixed zinc oxide and sulphur is which normally I charged into" the,hopper"16 is kept substantially full. The screw con- 20 end of the hopper into-theretort extension 12. Under normal operating conditions,

- the retort 12 and its extension 12 (below the 'screw conveyor 17 is substantially filled with the charge; The charge progresses by gravity downwardly through the; retort 12 as fast as the finished. product'is withdrawn from the bottom-of. the retort. To avoid danger of bridging and hanging of the 18 periodically strikes the retort'or its =.ex-

' tension, thus jarring the retort sufiiciently to keep the charge f1 eely, moving.

The retort 12 is heated to a temperature of about GOO-800 C. by the hot gases from half of the retort l2..serves as areaction chamber in which the conversion ,of zinc oxide to zincflsulphide takes place-J \Ve 40 have secured excellent results, by bringing g the'charge in this portion of the retort to a temperature of'about -700-725- G3 Substantially -complete ':onversiou of the zinc oxide to zinc sulphide takes place-in this portion of the'retort' The-lower half of the fretort 12 serves as the second stage heat i treatment chamberwhere the crude zinc sulphide product is subjectedto a heat. treatment operation asia consequence of which half of the retort 12 thanuin the upper half, 'and we have secured excellent results -wit-h a temperature the retort 12.9 1

.l y The sulphur dioxide gas evolved-bylthe reaction between the zinc oxide and sulphur providesa non-oxidizing atmospherein the retort 12, and furthermore maintains within the-retort a gaseous ressure sufficiently v greater than the atmospheric pressure to effectually prevent entrance. ofair into the retort. -The evolution of sulphur dioxide gas 18 of course greatest inthe'upper' por veyor 17 carries the mixture .from the lower- .charge in the retort,'the rapping mechanism .The upper oxidizing influences are present.

the color of the zinc sulphide is improved. The temperature of the charge in the lower may be slightly'less sul hide pigment.

. material, while a product.

tion' of the retort, butsuflic'ient gas is evolved even in the lower portion of the retort to provide a gaseous pressure slightly greater than the atmospheric pressure. 'li-loreover, the lower end is preferably sealed by the accumulation of. the discharged product in the pan 12 so that the entranqe of air into. the lower end of the retort is effectively guarded against. -10 advisable to secure a reasonably uniform vrotatably mounted star wheel'ha'ving four blades of wings. The shaft of the star Wheel The-star wheel discharge 19 comprises a is givenaquarter turn at predetermined intervals, preferably by'an automatic mechanical mechanism .ofany appropriate type. Each time the star wheel is turnedthrough. a quarter revolution a definite amount of,

pan, or the zinc sulphide product in the pan may beremoved through the door420, care being taken to avoid exposure ofth-e product to air while at a temperature above the oxidation temperature of zinesulphide, whichisinthe neighborhood of 400450? C.

The charge of mixed .zinc oxide and sul phur should be heated rapidly to a temperature that will insure complete reaction before volatilization losses have reduced the-amount of available sulphur below that chemically equivalentto the zinc oxide to be converted The temperature should be maintained. at I .the reaction point (in the first stage) only long enough to insure complete conversion'of the zinc oxide to zinc sulphide, and (in the second stage): only long enough to bring about the desired improvement in'the color of the zine sulphide. Continuation of the heating might result reoxidation of the zinc sulphide, particlarly if any air or other Excessive temperatures should be avoided as they result in a light sinteringtogether ,of 'the particles-and the particles at, the expenseof small particles.

Excessive temperatures also result in the early destruction of the retort-and contamination of the zinc sulphide product by scale, iron sulphide, etc, Control of the-temperature and of the time of heating permits the control of the particle size of the final zinc A short time of heating an 10w. temperature'yields fine particlesize long time of heating and high temperature causes the growth of particles and the sintering together of particles and The subsequent treatment of the zinc sulphide product collected in the pan 20 de pends-to some extent upon the use to which growth of large hencea relatively coarse final the zinc saphide pigmentis to tieut. The

product may, for example, be first screened and then subjected to-idry disintegration.

Ordinarily, it is our preferred-practice to wet grind the zinc sulphide product in a pebble mill'to break up aggregates. The ground-product is then filtered, dried and disintegrated.

The zinc sulphide pigment obtained by the foregoing procedure (using' zinc oxide of an average particle size of 0.25 'micron or less as a base) is awhite powder having no vi sible crystalline character even when examined under the highest magnification with the microscope. Its ultimate particles have an average diameter of the order of 0.5 micron. -It has strong pigment properties when rubbed down in oil, such as fineness, freedom from grit, and high hiding power or strength. In whiteness and bri htness, it is comparable with the best white pig- I ments available. The pigment is essentially pure zinc sulphide containing usually'less -than1% of free zinc oxide, and when made from substantially-pure starting materials :;contains only a few hundredths of one per cent of lead and iron."

While we have hereinbefore particularly described the operationof the apparatus illustrated in the accompanying drawing for carrying out a two-stage heat treatment operation, it is to be understood that in some cases the second stage may be dispensed with. The second stage heat treat-. ment operation improves the color of the zinc sulphide pigment. Where maximum whiteness and brightness are not required,

the charge" may be retained in theupright retort for only that period of time necessary to complete'the conversion of zinc oxide to zinc sulphide.

We claim: 1. The method of making a pigment com-, posed for the most part of zinc sulphide which comprises progressively passing a mixture of zinc oxide pigment and sulphur through an upright reaction chamber, and subjecting the mixture while passing through the chamber to a sufliciently high temperature to effect the ready formation of zinc sulphide. v

'2. The method of making a pigment composed for the most part of zinc, sulphide which comprises progressively passing a mixture of zinc oxide pigment and sulphur through a heated upright retort, and, subjecting themixture while passing through the retort toa temperature of 600-800 G.

3. The method of making a pigment composed for'the' most'part of zinc sulphide which comprises progressively passing a mixture of zinc oxide pigment of an average particle size not exceeding about 0.25 micron and sulphur through an upright reaction chamber, and subjecting the mixture while as a result of the reaction passing-through the chamber to a sufiiciently high temperature to efiect the ready formation of zinc sulphide.

4. The method of making a pigment composed for the most'part of zinc sulphide which comprises progressively passing a mixture of zinc oxide pigment of an average particle size not exceeding about 0.25 micron and sul hur through a heated upright re tort, su jecting the mixture while passing through the retort to a. temperature .of

GOO-800 C, and cooling the resulting pro- 4 duct under conditions inhibiting any ap .preciable oxidation of the zinc sulphide therein.

5. The method of making a pigment composed for the most part 'of zinc sulphide which comprises progressively passing a" mixture of -zinc.oxide pigment and'sul by gravity through a heated upright c amber in which a non-oxidizing atmosphere of slightly greater pressure than atmosphericpressure is maintained by the gases evolved oxide and sulphur, and cooling the resulting product under conditions inhibiting any appreciable. oxidation of the zinc sulphide th'erein.

6. The method of making a pigment composed for the most part of zinc sulphide which comprises progressively passing a between-the zinc mixture of zinc oxide pigment and sulphur by gravity through a heated upright chamber in which a non-oxidizing atmosphereof slightly greater pressure than atmospheric pressure is maintained by the gases evolved as a result of the reaction'between the zinc f oxide and sulphur, progressively discharging the resulting product from the bottom of the-chamber, sealingthe chamber at the v bottom against the entrance of air, and cooling the resulting product under conditions inhibiting any apprec1able oxidation of the zinc sulphide therein.

7 The method of making a" pigment composed for the most part of zinc sulphide which comprises progressively passing a mixture of zinc'oxide pigmentfand sulphur through an upright reaction chamber,

and subjecting the mixture while passing through the chamber to a two-stage heat.

treatment operation in the first stage of which substantially complete conversion of zinc oxide to-zinc sulphide is efi'ected and 1 operation under non-oxidizing conditions n and at a temperature of 600800 C., subpart of zinc sulphide stantially complete conversion of zinc oxide to zinc sulphide being effected in the first stage of said operation and an improvement in the color of the zinc sulphide being attained in the second stage, and cooling the resulting product under conditions inhibiting any appreciable oxidation of the zinc sulphide therein.

.' V 9. The method of making a pigment composed for the most part of zinc sulphide which comprises progressively passing a mixture of zinc oxide pigment of an average particle size not exceeding about 0.25 micron and sulphur through an upright reaction chamber,'subjecting the mixture While passing through the chamber to a two-stage heat-treatment operation in the first stage of which substantially complete conversion of V zinc oxide to zinc sulphide is effected and-in the second stage of which an improvement in the color of the zinc sulphide is attained, and cooling the resulting product under con ditions inhibiting any appreciable oxidation of the zinc sulphide therein.

10. The method of making a pigment composed for the most part of zinc sulphide which comprises progressively passing a mixture of zinc oxide pigment of an average particle size not exceeding about Q25 micron and sulphur through an upright reaction chamber, subjecting the mixture while passing through the chamber to a twostage heat treatment operation under nonoxidizing conditions and at a temperature of 600800 0., substantially complete conversion of zinc oxide to zinc sulphide being eflected in the first stage of said operation mixture of zinc oxide pigment and sulphur I by gravity through an upright chamber heated to a temperature of GOO-800C. and r in which a non-oxidizing atmosphere is maintained by" the gases evolved as a result of the reaction between the zinc oxide and sulphur, and cooling the resulting product under conditions inhibiting any'appreciable oxidation of the zinc sulphide therein.

12. The method of making a pigment composed for the most part of zinc sulphide which comprises progressively passing a mixture of zinc oxide pigment of an average particle size not exceeding about 0.25 micron and sulphur through an uprightichamber heated to a temperature of 600800 C. and in which a non-oxidizing atmosphere is maintained. by the gases evolved as a result of the reaction between the zinc oxide and sulphur, progressively discharging the resulting product from the bottom of the chamber, and cooling the resulting-product under conditions inhibiting any appreciable oxidation of the zinc sulphide therein.

In testimony whereof we aifix our signatures.

FRANK G. BREYER.

CLAYTON W. FAR-BER. 7 

